US20090188316A1 - Resistive Hydrogen Sensor - Google Patents
Resistive Hydrogen Sensor Download PDFInfo
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- US20090188316A1 US20090188316A1 US12/360,589 US36058909A US2009188316A1 US 20090188316 A1 US20090188316 A1 US 20090188316A1 US 36058909 A US36058909 A US 36058909A US 2009188316 A1 US2009188316 A1 US 2009188316A1
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- layer
- resistance layer
- hydrogen sensor
- resistance
- resistive
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 72
- 239000001257 hydrogen Substances 0.000 title claims abstract description 72
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims abstract description 8
- 229910052729 chemical element Inorganic materials 0.000 claims abstract description 8
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 43
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 238000002161 passivation Methods 0.000 claims description 21
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- 239000010408 film Substances 0.000 claims description 14
- 239000000446 fuel Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000003491 array Methods 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/005—H2
Definitions
- the invention relates to a resistive hydrogen sensor, which has at least two electrical connections and at least one resistance layer that alters its electrical resistance upon hydrogen absorption, wherein the electrical connections are connected to each other via the resistance layer.
- Such a hydrogen sensor is disclosed in Sakamoto, Y. et al., “Electrical restistance [sic] measurements as a function of composition of palladium-hydrogen(deuterium) systems by a gas phase method”, J. Phys.: Condens. Matter 8 (1996), pp. 3399-3411.
- the hydrogen sensor has a palladium film with a thickness of 50-60 ⁇ m, which is cut into ca. 2 mm ⁇ 5 mm strips.
- the resistance layer is arranged in a stainless steel reaction vessel, which is connected via feed lines to a hydrogen and a deuterium reservoir.
- the electrical resistance of the hydrogen-free palladium film is around 4.682 ⁇ 0.1067 m ⁇ at a temperature of 273 K. If the palladium film is exposed at room temperature to a hydrogen atmosphere with a pressure of one bar, its specific resistance changes by about 80% in comparison to a hydrogen-free palladium film.
- a disadvantage resides in the hydrogen sensor in that the electrical resistance of the palladium film is only relatively low, so that the resistance of the feed lines, which connect the connections to the palladium film, has a substantial effect on the measurement.
- a hydrogen sensor of the aforesaid type is also disclosed in Wang, Min et al.: “Palladium-silver thin film for hydrogen sensing”, Sensors and Actuators B 123 (2007), pp. 101-106, which has a resistance layer composed of a palladium-silver alloy, which is applied to a ceramic substrate via a thin film process. Compared to a resistance layer of pure palladium, the palladium-silver provides greater stability in the hydrogen incorporation.
- the resistance layer is configured with a meandering shape in order to increase electrical resistance.
- the disadvantage herein resides in that the resistance layer covers a relatively large surface area on the substrate. In spite of the meandering configuration, the electrical resistance of the resistance layer is still relatively low in this hydrogen sensor as well.
- the object is therefore to create a hydrogen sensor of the aforesaid type with compact dimensions that enables a high measuring sensitivity.
- the resistance layer adjoins a contact layer, which contains at least one chemical element from the fourth subgroup of the periodic table and/or carbon, and in that the contact layer is connected in series between the electrical connections to the resistance layer.
- the contact resistance at the interface between the resistance layer and the contact layer also changes in an advantageous manner in response to a change in hydrogen concentration. This results in a marked change of the electrical resistance between the connectors of the hydrogen sensor and thus a greater measuring sensitivity.
- the hydrogen sensor can be manufactured via the process steps known to semiconductor manufacturing technology with compact dimensions by applying the resistance layer to a substrate, for example, a silicon substrate. Owing to the increased sensitivity compared to standard resistive hydrogen sensors, the resistance layer can be connected to the electrical connections via conductor paths with relatively small cross-sections. Preference is given to integration of the conductor paths on and/or in the substrate. The hydrogen sensor can thus be manufactured economically and with compact dimensions.
- the chemical element of the fourth subgroup of the periodic table, of which there is at least one, can be in particular hafnium or zirconium.
- the contact layer is composed of titanium or contains titanium and/or a titanium-containing chemical compound.
- a particularly high measuring sensitivity can be achieved with such a contact layer.
- titanium is comparatively economical to obtain.
- the resistance layer is arranged on a substrate, wherein the contact layer of the resistance layer is covered, at least area-wise, so that at least a partial area of the resistance layer is arranged between the interface and the substrate.
- the sequence of layers comprising the resistance layer and the contact layer thus permits a relatively large interface between the resistance layer and the contact layer, even with low film thicknesses.
- the contact layer is advantageously covered with a passivation layer. This prevents oxidation of the contact layer when the hydrogen sensor comes into contact with atmospheric oxygen.
- the resistance layer being composed of palladium or having a palladium-containing alloy and/or a palladium-containing chemical compound.
- the hydrogen sensor then enables an even greater measuring sensitivity.
- the resistance layer contains a suitable chemical compound for incorporating hydrogen formed from a first chemical element A and a second chemical element B, which is of the type AB 2 or AB 5 .
- a suitable chemical compound for incorporating hydrogen formed from a first chemical element A and a second chemical element B, which is of the type AB 2 or AB 5 .
- the passivation layer is a metallic layer that adjoins a second interface on the resistance layer, and if the passivation layer is connected in series between the electrical connections to the contact layer and the resistance layer, and is preferably made of gold. With a current flow between the electrical connections, a voltage drop dependent on the hydrogen concentration in the resistance layer occurs on the first interface formed between the resistance layer and the contact layer and/or on the second interface formed between the contact layer and the passivation layer. The hydrogen sensor thus enables an even stronger measuring signal at the electrical connections.
- the contact layer is configured as a thin film having a layer thickness of less than 300 ⁇ m, particularly less than 200 ⁇ m, and preferably less than 100 ⁇ m.
- the hydrogen sensor can then be economically produced by standard semiconductor manufacturing processes, for example, on a silicon substrate. The hydrogen sensor thus permits very compact dimensions.
- At least a partial area of the contact layer is arranged between the resistance layer and the substrate.
- the resistance layer thus also serves as passivation for the contact layer as well as a means for generating the measuring signal.
- At least two of the layer arrays consisting in each case of at least the resistance layer, the adjoining contact layer, and where applicable the passivation layer adjoining the latter, are arranged on the substrate, wherein said layer arrays are connected in series between the electrical connections.
- the hydrogen sensor then enables an even stronger measuring signal, wherein the total measuring signal corresponds to the sum of the partial measuring signals generated on the individual layer arrays.
- the resistance layer has at least one surface zone contacting the atmosphere, wherein preference is given to said surface zone laterally adjoining the interface situated between the resistance layer and the contact layer.
- the hydrogen sensor can then be used to detect gaseous hydrogen in the environment. By continuous measuring of the electrical resistance between the connections of the hydrogen sensor, the partial pressure of the hydrogen in the environment can be distinctly determined. If the surface zone in contact with the atmosphere is adjacent to the interface, the hydrogen can reach the interface from the surface zone via short diffusion paths. The measuring signal of the hydrogen sensor then reacts quickly to changes in the hydrogen partial pressure.
- the resistance layer is a hydrogen storage unit connected to a fuel cell and the electrical connections are connected to an evaluator, which is configured as a charge level indicator for the hydrogen storage unit. Preference is given to the evaluator having a display for charge level. This permits easy checking of the charge level of the hydrogen storage unit and/or easy measurement of the volume of hydrogen incorporated in the hydrogen storage unit.
- the fuel cell has a layer stack consisting of at least two electrode layers and an membrane layer situated between them, and if the resistance layer is arranged, at least area-wise, between said layer stack and the substrate.
- the membrane layer is an ion-conducting layer, preferably a polymer-electrolyte membrane.
- FIG. 1 shows a cross-section through a first illustrative embodiment of a hydrogen sensor
- FIG. 2 shows a view from above of the hydrogen sensor shown in FIG. 1 ,
- FIG. 3 is a diagrammatic illustration showing adsorption of hydrogen on the surface of a palladium film and absorption of hydrogen by the palladium film of the hydrogen gas sensor
- FIG. 4 shows a cross-section through a second illustrative embodiment of the hydrogen sensor
- FIG. 5 shows a view from above of the hydrogen sensor shown in FIG. 4 .
- FIG. 6 shows a cross-section through a third embodiment of the hydrogen sensor integrated in a fuel cell, wherein an electrical consumer connected to the fuel cell is schematically represented by a resistance symbol.
- a resistive hydrogen sensor designated in entirety by 1 in FIG. 1 has a substrate 2 , on which are arranged a resistance layer 3 composed of palladium or a palladium alloy, two electrical contact layers 4 a, 4 b composed of titanium, and two passivation layers 5 a, 5 b.
- the passivation layers 5 a, 5 b are composed of an electrically conductive material, preferably a noble metal, particularly gold and in each case they have a partial area serving as an electrical connection 6 , 7 .
- a current source for an evaluator (not shown in any greater detail in the drawing) is connected to the connectors 6 , 7 .
- the substrate can be an electrically conductive substrate with passivation layers, a semiconductor substrate, such as, e.g., a silicon substrate, or an electrically insulating substrate, for example a ceramic substrate or a plastic substrate.
- each contact layer 4 a, 4 b adjoins a first interface 8 a, 8 b on the resistance layer 3 and a second interface 9 a, 9 b separated therefrom on the passivation layer 5 a, 5 b.
- the passivation layers 5 a, 5 b, the contact layers 4 a, 4 b, and the resistance layer 3 are connected in series between the connections 6 , 7 in such a way that an electric current flowing between the connections 6 , 7 permeates the first interfaces 8 a, 8 b and the second interfaces 9 a, 9 b.
- each contact layer 4 a, 4 b in each case cover one of these border areas with a partial area.
- Another partial area of each contact layer 4 a, 4 b is in each case directly arranged on the substrate 2 .
- the contact layers 4 a, 4 b in each case have a step-like or ledge-like outline.
- the passivation layer 5 a, 5 b covers its allocated contact layer 4 a, 4 b completely in each case.
- the passivation layer 5 a, 5 b thus conforms to the step-like or ledge-like outline of the underlying contact layer 4 a, 4 b.
- the passivation layer 5 a, 5 b and the contact layer 4 a, 4 b are in each case configured as thin films.
- the film thickness of the passivation layer 5 a, 5 b and the contact layer 4 a, 4 b can be, for example, around 100 ⁇ m.
- the passivation layer 5 a, 5 b and the contact layer 4 a, 4 b in each case have a greater width at the connections 6 , 7 and the partial area covering the resistance layer 3 than in a section situated between the connections 6 , 7 and the partial area covering the resistance layer 3 .
- the resistance layer 3 has a surface zone 10 contacting the atmosphere. This surface zone 10 laterally adjoins the first interface 8 a, 8 b situated between the resistance layer 3 and the respective contact layer 4 a, 4 b.
- the gaseous hydrogen molecules H 2 located in the vicinity of the surface zone 10 can be adsorbed on the surface zone 10 in the form of hydrogen atoms H ad .
- the hydrogen atoms H ad are absorbed by the resistance layer 3 and incorporate themselves in the latter. In the resistance layer 3 the absorbed hydrogen atoms H ab diffuse to the first interfaces 8 a, 8 b and where applicable to the second interfaces 9 a, 9 b.
- a plurality of layer arrays 11 is arranged on the substrate 2 , said arrays in each case comprising the resistance layer 3 , the contact layer 4 a, 4 b adjoining it on the first interface 8 a, 8 b, and the passivation layer 5 a, 5 b adjoining the contact layer 4 a, 4 b on the second interface 9 a, 9 b. It can be clearly discerned that these layer arrays 11 are connected in series between the connections 6 , 7 in such a way that the electric current applied to the connections 6 , 7 by the current source flows through all first interfaces 8 a, 8 b and through at least two of the second interfaces 9 a, 9 b.
- the resistance layer is configured as a thick film, which serves as a hydrogen storage unit for a fuel cell 12 .
- the electrical connections 6 , 7 are connected to an evaluator, which is not shown in any greater detail in the drawing and which is configured as a charge level indicator for the hydrogen storage unit.
- the evaluator can be integrated in the substrate 2 as an electronic circuit.
- the fuel cell is configured as a layer stack, which has two electrode layers 13 , 14 and a membrane layer 15 situated between them.
- a first electrode layer 13 acts as a cathode and a second electrode layer 14 in contact with an oxygen-containing atmosphere acts as an anode.
- the membrane layer 15 is configured as a polymer-electrolyte membrane.
- the layer stack is arranged on the resistance layer 3 between the first interfaces 8 a, 8 b. Between the electrode layers 13 , 14 there is an electric voltage which can be measured.
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Abstract
Description
- The invention relates to a resistive hydrogen sensor, which has at least two electrical connections and at least one resistance layer that alters its electrical resistance upon hydrogen absorption, wherein the electrical connections are connected to each other via the resistance layer.
- Such a hydrogen sensor is disclosed in Sakamoto, Y. et al., “Electrical restistance [sic] measurements as a function of composition of palladium-hydrogen(deuterium) systems by a gas phase method”, J. Phys.: Condens. Matter 8 (1996), pp. 3399-3411. As a resistance layer, the hydrogen sensor has a palladium film with a thickness of 50-60 μm, which is cut into ca. 2 mm×5 mm strips. The resistance layer is arranged in a stainless steel reaction vessel, which is connected via feed lines to a hydrogen and a deuterium reservoir. Nickel wires with a diameter of about 0.3 mm, which connect the resistance layer to electrical connections arranged on the outside of the reaction vessel, are welded onto the resistance layer. Electrical insulation for the nickel wires is provided by glass tubes, which are connected to the reaction vessel. The electrical resistance of the hydrogen-free palladium film is around 4.682±0.1067 mΩ at a temperature of 273 K. If the palladium film is exposed at room temperature to a hydrogen atmosphere with a pressure of one bar, its specific resistance changes by about 80% in comparison to a hydrogen-free palladium film. A disadvantage resides in the hydrogen sensor in that the electrical resistance of the palladium film is only relatively low, so that the resistance of the feed lines, which connect the connections to the palladium film, has a substantial effect on the measurement. Since the electrical resistance of the feed lines increases as the cross-section of the lines decreases, miniaturization of the hydrogen sensor is only possible to a limited extent. If the cross-section of the feed lines is made too small, the electrical resistance between the connections of the hydrogen sensor is then essentially defined solely by the feed lines. Temperature changes, which affect the electrical resistance of the palladium film and the feed lines, can also lead to measurement errors.
- A hydrogen sensor of the aforesaid type is also disclosed in Wang, Min et al.: “Palladium-silver thin film for hydrogen sensing”, Sensors and Actuators B 123 (2007), pp. 101-106, which has a resistance layer composed of a palladium-silver alloy, which is applied to a ceramic substrate via a thin film process. Compared to a resistance layer of pure palladium, the palladium-silver provides greater stability in the hydrogen incorporation. The resistance layer is configured with a meandering shape in order to increase electrical resistance. The disadvantage herein, however, resides in that the resistance layer covers a relatively large surface area on the substrate. In spite of the meandering configuration, the electrical resistance of the resistance layer is still relatively low in this hydrogen sensor as well.
- The object is therefore to create a hydrogen sensor of the aforesaid type with compact dimensions that enables a high measuring sensitivity.
- This object is achieved for the invention in that on at least one interface the resistance layer adjoins a contact layer, which contains at least one chemical element from the fourth subgroup of the periodic table and/or carbon, and in that the contact layer is connected in series between the electrical connections to the resistance layer.
- In addition to the electrical resistance of the resistance layer, the contact resistance at the interface between the resistance layer and the contact layer also changes in an advantageous manner in response to a change in hydrogen concentration. This results in a marked change of the electrical resistance between the connectors of the hydrogen sensor and thus a greater measuring sensitivity. The hydrogen sensor can be manufactured via the process steps known to semiconductor manufacturing technology with compact dimensions by applying the resistance layer to a substrate, for example, a silicon substrate. Owing to the increased sensitivity compared to standard resistive hydrogen sensors, the resistance layer can be connected to the electrical connections via conductor paths with relatively small cross-sections. Preference is given to integration of the conductor paths on and/or in the substrate. The hydrogen sensor can thus be manufactured economically and with compact dimensions. The chemical element of the fourth subgroup of the periodic table, of which there is at least one, can be in particular hafnium or zirconium.
- In a preferred embodiment of the invention, the contact layer is composed of titanium or contains titanium and/or a titanium-containing chemical compound. A particularly high measuring sensitivity can be achieved with such a contact layer. Furthermore, titanium is comparatively economical to obtain.
- In an advantageous embodiment of the invention, the resistance layer is arranged on a substrate, wherein the contact layer of the resistance layer is covered, at least area-wise, so that at least a partial area of the resistance layer is arranged between the interface and the substrate. The sequence of layers comprising the resistance layer and the contact layer thus permits a relatively large interface between the resistance layer and the contact layer, even with low film thicknesses.
- The contact layer is advantageously covered with a passivation layer. This prevents oxidation of the contact layer when the hydrogen sensor comes into contact with atmospheric oxygen.
- Preference is given to the resistance layer being composed of palladium or having a palladium-containing alloy and/or a palladium-containing chemical compound. The hydrogen sensor then enables an even greater measuring sensitivity.
- In another advantageous embodiment of the invention, the resistance layer contains a suitable chemical compound for incorporating hydrogen formed from a first chemical element A and a second chemical element B, which is of the type AB2 or AB5. With such a resistance layer it is also possible to achieve a high measuring sensitivity.
- It is advantageous if the passivation layer is a metallic layer that adjoins a second interface on the resistance layer, and if the passivation layer is connected in series between the electrical connections to the contact layer and the resistance layer, and is preferably made of gold. With a current flow between the electrical connections, a voltage drop dependent on the hydrogen concentration in the resistance layer occurs on the first interface formed between the resistance layer and the contact layer and/or on the second interface formed between the contact layer and the passivation layer. The hydrogen sensor thus enables an even stronger measuring signal at the electrical connections.
- In a preferred embodiment of the invention, the contact layer is configured as a thin film having a layer thickness of less than 300 μm, particularly less than 200 μm, and preferably less than 100 μm. The hydrogen sensor can then be economically produced by standard semiconductor manufacturing processes, for example, on a silicon substrate. The hydrogen sensor thus permits very compact dimensions.
- In a possible embodiment of the invention, at least a partial area of the contact layer is arranged between the resistance layer and the substrate. The resistance layer thus also serves as passivation for the contact layer as well as a means for generating the measuring signal.
- In a further embodiment of the invention, at least two of the layer arrays consisting in each case of at least the resistance layer, the adjoining contact layer, and where applicable the passivation layer adjoining the latter, are arranged on the substrate, wherein said layer arrays are connected in series between the electrical connections. The hydrogen sensor then enables an even stronger measuring signal, wherein the total measuring signal corresponds to the sum of the partial measuring signals generated on the individual layer arrays.
- In a preferred embodiment of the invention, the resistance layer has at least one surface zone contacting the atmosphere, wherein preference is given to said surface zone laterally adjoining the interface situated between the resistance layer and the contact layer. The hydrogen sensor can then be used to detect gaseous hydrogen in the environment. By continuous measuring of the electrical resistance between the connections of the hydrogen sensor, the partial pressure of the hydrogen in the environment can be distinctly determined. If the surface zone in contact with the atmosphere is adjacent to the interface, the hydrogen can reach the interface from the surface zone via short diffusion paths. The measuring signal of the hydrogen sensor then reacts quickly to changes in the hydrogen partial pressure.
- In another advantageous embodiment of the invention, the resistance layer is a hydrogen storage unit connected to a fuel cell and the electrical connections are connected to an evaluator, which is configured as a charge level indicator for the hydrogen storage unit. Preference is given to the evaluator having a display for charge level. This permits easy checking of the charge level of the hydrogen storage unit and/or easy measurement of the volume of hydrogen incorporated in the hydrogen storage unit.
- It is advantageous if the fuel cell has a layer stack consisting of at least two electrode layers and an membrane layer situated between them, and if the resistance layer is arranged, at least area-wise, between said layer stack and the substrate. This results in a highly compact arrangement in which the fuel cell is arranged on the hydrogen sensor, thus conserving chip surface area. The membrane layer is an ion-conducting layer, preferably a polymer-electrolyte membrane.
- Illustrative embodiments of the invention are explained in more detail in the following, wherein:
-
FIG. 1 shows a cross-section through a first illustrative embodiment of a hydrogen sensor, -
FIG. 2 shows a view from above of the hydrogen sensor shown inFIG. 1 , -
FIG. 3 is a diagrammatic illustration showing adsorption of hydrogen on the surface of a palladium film and absorption of hydrogen by the palladium film of the hydrogen gas sensor, -
FIG. 4 shows a cross-section through a second illustrative embodiment of the hydrogen sensor, -
FIG. 5 shows a view from above of the hydrogen sensor shown inFIG. 4 , and -
FIG. 6 shows a cross-section through a third embodiment of the hydrogen sensor integrated in a fuel cell, wherein an electrical consumer connected to the fuel cell is schematically represented by a resistance symbol. - A resistive hydrogen sensor designated in entirety by 1 in
FIG. 1 has asubstrate 2, on which are arranged aresistance layer 3 composed of palladium or a palladium alloy, twoelectrical contact layers passivation layers - The passivation layers 5 a, 5 b are composed of an electrically conductive material, preferably a noble metal, particularly gold and in each case they have a partial area serving as an
electrical connection connectors - In each case each
contact layer first interface 8 a, 8 b on theresistance layer 3 and asecond interface 9 a, 9 b separated therefrom on thepassivation layer resistance layer 3 are connected in series between theconnections connections first interfaces 8 a, 8 b and thesecond interfaces 9 a, 9 b. - It can be discerned in
FIGS. 1 and 2 that theinterfaces 8 a, 8 b are arranged on border areas of theresistance layer 3 separated from each other, and that the contact layers 4 a, 4 b in each case cover one of these border areas with a partial area. Another partial area of eachcontact layer substrate 2. Between the partial area covering theresistance layer 3 and the partial area adjoining thesubstrate 2, the contact layers 4 a, 4 b in each case have a step-like or ledge-like outline. - The
passivation layer contact layer passivation layer underlying contact layer passivation layer contact layer passivation layer contact layer - It can also be discerned in
FIG. 2 that thepassivation layer contact layer connections resistance layer 3 than in a section situated between theconnections resistance layer 3. - Between the contact layers 4 a, 4 b, the
resistance layer 3 has asurface zone 10 contacting the atmosphere. Thissurface zone 10 laterally adjoins thefirst interface 8 a, 8 b situated between theresistance layer 3 and therespective contact layer - It can be discerned in
FIG. 3 that the gaseous hydrogen molecules H2 located in the vicinity of thesurface zone 10 can be adsorbed on thesurface zone 10 in the form of hydrogen atoms Had. The hydrogen atoms Had are absorbed by theresistance layer 3 and incorporate themselves in the latter. In theresistance layer 3 the absorbed hydrogen atoms Hab diffuse to thefirst interfaces 8 a, 8 b and where applicable to thesecond interfaces 9 a, 9 b. - In the illustrative embodiment shown in
FIGS. 4 and 5 , a plurality oflayer arrays 11 is arranged on thesubstrate 2, said arrays in each case comprising theresistance layer 3, thecontact layer first interface 8 a, 8 b, and thepassivation layer contact layer second interface 9 a, 9 b. It can be clearly discerned that theselayer arrays 11 are connected in series between theconnections connections first interfaces 8 a, 8 b and through at least two of thesecond interfaces 9 a, 9 b. - In the illustrative embodiment shown in
FIG. 6 , the resistance layer is configured as a thick film, which serves as a hydrogen storage unit for afuel cell 12. Theelectrical connections substrate 2 as an electronic circuit. - The fuel cell is configured as a layer stack, which has two
electrode layers membrane layer 15 situated between them. Afirst electrode layer 13 acts as a cathode and asecond electrode layer 14 in contact with an oxygen-containing atmosphere acts as an anode. Themembrane layer 15 is configured as a polymer-electrolyte membrane. The layer stack is arranged on theresistance layer 3 between thefirst interfaces 8 a, 8 b. Between the electrode layers 13, 14 there is an electric voltage which can be measured.
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US9664633B2 (en) | 2017-05-30 |
EP2083262B1 (en) | 2014-05-07 |
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